CN102101691B - Preparation method of cerium oxide nanoparticles - Google Patents
Preparation method of cerium oxide nanoparticles Download PDFInfo
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- CN102101691B CN102101691B CN200910243664XA CN200910243664A CN102101691B CN 102101691 B CN102101691 B CN 102101691B CN 200910243664X A CN200910243664X A CN 200910243664XA CN 200910243664 A CN200910243664 A CN 200910243664A CN 102101691 B CN102101691 B CN 102101691B
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- 229910000420 cerium oxide Inorganic materials 0.000 title claims abstract description 65
- BMMGVYCKOGBVEV-UHFFFAOYSA-N oxo(oxoceriooxy)cerium Chemical compound [Ce]=O.O=[Ce]=O BMMGVYCKOGBVEV-UHFFFAOYSA-N 0.000 title claims abstract description 44
- 239000002105 nanoparticle Substances 0.000 title claims abstract description 27
- 238000002360 preparation method Methods 0.000 title claims abstract description 20
- 239000002245 particle Substances 0.000 claims abstract description 43
- 150000000703 Cerium Chemical class 0.000 claims abstract description 27
- 238000006243 chemical reaction Methods 0.000 claims abstract description 19
- 239000007788 liquid Substances 0.000 claims abstract description 18
- 239000006185 dispersion Substances 0.000 claims abstract description 14
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 10
- 238000011282 treatment Methods 0.000 claims abstract description 7
- 230000001590 oxidative effect Effects 0.000 claims abstract description 5
- HSJPMRKMPBAUAU-UHFFFAOYSA-N cerium(3+);trinitrate Chemical compound [Ce+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O HSJPMRKMPBAUAU-UHFFFAOYSA-N 0.000 claims abstract description 4
- 150000001875 compounds Chemical class 0.000 claims description 31
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 28
- 238000000265 homogenisation Methods 0.000 claims description 20
- 238000000034 method Methods 0.000 claims description 17
- GWXLDORMOJMVQZ-UHFFFAOYSA-N cerium Chemical compound [Ce] GWXLDORMOJMVQZ-UHFFFAOYSA-N 0.000 claims description 13
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 12
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical group CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 12
- 229910052684 Cerium Inorganic materials 0.000 claims description 11
- 239000007864 aqueous solution Substances 0.000 claims description 11
- 239000000243 solution Substances 0.000 claims description 10
- 239000002904 solvent Substances 0.000 claims description 8
- 239000000314 lubricant Substances 0.000 claims description 6
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 4
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 claims description 4
- 150000001335 aliphatic alkanes Chemical group 0.000 claims description 4
- 150000001412 amines Chemical class 0.000 claims description 4
- ZBCBWPMODOFKDW-UHFFFAOYSA-N diethanolamine Chemical compound OCCNCCO ZBCBWPMODOFKDW-UHFFFAOYSA-N 0.000 claims description 4
- 238000005984 hydrogenation reaction Methods 0.000 claims description 4
- 230000035484 reaction time Effects 0.000 claims description 4
- 229960004418 trolamine Drugs 0.000 claims description 4
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical group [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 3
- 229910052760 oxygen Inorganic materials 0.000 claims description 3
- 239000001301 oxygen Substances 0.000 claims description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims description 2
- 125000002029 aromatic hydrocarbon group Chemical group 0.000 claims description 2
- 229910052799 carbon Inorganic materials 0.000 claims description 2
- 230000002349 favourable effect Effects 0.000 claims description 2
- 238000011049 filling Methods 0.000 claims description 2
- 229910052757 nitrogen Inorganic materials 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 abstract description 6
- 238000007254 oxidation reaction Methods 0.000 abstract description 5
- 238000011065 in-situ storage Methods 0.000 abstract description 2
- 150000002894 organic compounds Chemical class 0.000 abstract 2
- 239000007800 oxidant agent Substances 0.000 abstract 2
- VYLVYHXQOHJDJL-UHFFFAOYSA-K cerium trichloride Chemical compound Cl[Ce](Cl)Cl VYLVYHXQOHJDJL-UHFFFAOYSA-K 0.000 abstract 1
- 231100000989 no adverse effect Toxicity 0.000 abstract 1
- 238000013341 scale-up Methods 0.000 abstract 1
- -1 nitrogenous compound Chemical class 0.000 description 16
- 239000007787 solid Substances 0.000 description 9
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 8
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- 235000011114 ammonium hydroxide Nutrition 0.000 description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- 125000000217 alkyl group Chemical group 0.000 description 4
- 125000004432 carbon atom Chemical group C* 0.000 description 4
- 239000002283 diesel fuel Substances 0.000 description 4
- 239000003350 kerosene Substances 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 230000003647 oxidation Effects 0.000 description 4
- 238000001556 precipitation Methods 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- 239000004530 micro-emulsion Substances 0.000 description 3
- 0 CC(C)(*)NC(c1nc(C(NC(C)(C)*)=O)ccc1)=O Chemical compound CC(C)(*)NC(c1nc(C(NC(C)(C)*)=O)ccc1)=O 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 239000012074 organic phase Substances 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 229910052761 rare earth metal Inorganic materials 0.000 description 2
- 150000002910 rare earth metals Chemical class 0.000 description 2
- 238000004381 surface treatment Methods 0.000 description 2
- 239000012756 surface treatment agent Substances 0.000 description 2
- 239000011358 absorbing material Substances 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 230000003321 amplification Effects 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 238000003837 high-temperature calcination Methods 0.000 description 1
- 238000001027 hydrothermal synthesis Methods 0.000 description 1
- 150000002466 imines Chemical group 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 229910017053 inorganic salt Inorganic materials 0.000 description 1
- 238000009434 installation Methods 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- 238000003199 nucleic acid amplification method Methods 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000003980 solgel method Methods 0.000 description 1
- 238000005979 thermal decomposition reaction Methods 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
Landscapes
- Compounds Of Alkaline-Earth Elements, Aluminum Or Rare-Earth Metals (AREA)
Abstract
The invention relates to a preparation method of cerium oxide nanoparticles, which comprises the steps of dissolving a coordinatable organic compound in nonpolar oil at a mass concentration of 10-50% to prepare a cerium chloride or cerium nitrate solution, wherein the mass concentration is 5-30%; adding a coordinatable organic compound and trivalent inorganic cerium salt into high-speed homogenizing equipment or supergravity reaction equipment according to the mol ratio of 1-3: 1 for reaction, adding an oxidant into liquid of the equipment for oxidation reaction, wherein the mol ratio of the oxidant to the trivalent inorganic cerium salt is 1.5-2.5: 1, and after the reaction is finished, centrifuging to remove a water layer to obtain cerium oxide nanoparticles with the particle size of 5-100 nanometers; the nanometer cerium oxide obtained by combining a high-shear strong-dispersion reactor and a nanometer particle surface in-situ treatment technology has uniform particle size and can form a stable dispersion system in nonpolar oil; the preparation process is simple and short, the post-treatment is simple, no adverse effect is caused to the environment, and the industrial scale-up production is easy to realize.
Description
Technical field
The present invention relates to a kind of preparation method of rare earth material, particularly be prepared in the method for the cerium oxide nano particle of stable dispersion in the non-polar oil through coordination-oxidizing reaction.
Background technology
Cerium oxide is a kind of rare earth material in numerous areas widespread uses such as uv-absorbing material, gas sensor, optical material, fuel cell, photochemical catalytic oxidation, automobile engine tail gas processing.In recent years; People have carried out more deep research to the nano-cerium oxide particle; There is several different methods can be used to prepare the nano-cerium oxide particle, like high-temperature calcination, hydrothermal synthesis method, solution deposit, sol-gel method, reverse microemulsion process, sonochemistry method, organic cerium salt thermal decomposition method etc.
Although the bibliographical information of relevant preparation cerium oxide nano particle many (as: J.Am.Ceram.Soc.1993,76,1577.; Appl.Phys.Lett.2002,80,127.; J.Mater.Chem.2000,10,473.; J.Mater.Sci.Lett.2002,21,489.; Chem.Commun.1999,957. etc.), but make uniform and stablely, the cerium oxide nano particle that particularly in the more weak oil of polarity, still has better dispersing property is the comparison difficulty.At present, it is even to utilize reverse microemulsion process to make particle diameter, the nano-cerium oxide particle of stably dispersing; But this method suitability for industrialized production will the time face many difficulties (Nat.Mater.2004,3,891); For example, the concentration of cerium oxide is very low in the reverse micro emulsion, needs a large amount of organic solvents during production; Can cause complex manufacturing, processing cost is too high, and this all brings very big pressure to production cost control and environment protection.
Summary of the invention
The purpose of this invention is to provide a kind of can be in non-polar oil the cerium oxide nano particle preparation method of stable dispersion; Utilize this method not only can obtain uniform particles, dispersing property good, can be as the cerium oxide nano particle of non-polar oil additive, and easy realization of industrial production.
Of the present invention a kind of can be in non-polar oil the cerium oxide nano particle preparation method of stable dispersion; It is characterized in that with cerous inorganic salt be raw material; But the coordination organic cpds of first and nitrogenous or oxygen or sulfur heteroatom generates the trivalent cerium coordination compound through coordination chemistry; Under alkaline condition, carry out oxidation then and form, reaction mass all is in the high shear field environment in whole process, and concrete working method is:
1, at first but the mass concentration of coordination organic cpds with 10-50% is dissolved in the non-polar oil, and this solution is added in high speed homogenization equipment or the hypergravity conversion unit;
2, the aqueous solution or the methanol solution or the ethanolic soln of the inorganic cerium salt of trivalent of preparation Cerium II Chloride or cerous nitrate, the mass concentration that makes the inorganic cerium solution of trivalent is 5-30%;
3, the inorganic cerium solution of trivalent is joined in high speed homogenization equipment or the hypergravity conversion unit; And but the mol ratio that makes coordination organic cpds and the inorganic cerium salt of trivalent is 1～3: 1, and opertaing device temperature 40-60 degree is sheared 800-25000 rev/min of rotating speed; Reaction times is 30-120 minute; After the end, add alkaline matter, make the pH value of liquid reach 8～10;
4, in the liquid of equipment, add oxygenant and carry out oxidizing reaction; The mol ratio of the inorganic cerium salt of oxygenant and trivalent is 1.5-2.5: 1; Reaction times 30-120 minute, shear 800-25000 rev/min of rotating speed, after the end; The centrifugal water layer of removing promptly obtains the cerium oxide nano particle of particle diameter within the 5-100 nanometer range.
But described coordination organic cpds is the compound that comprises the electron rich group of nitrogen or oxygen or sulfur heteroatom or heteroatomic ring structure or imine structure in the molecular structure; Contain long chain alkane structure in the molecule simultaneously greater than 8 carbon; And these electron rich groups can form stable coordination compound through coordination with cerium atom; Guarantee its favorable solubility in non-polar oil, the general formula of this compounds is following:
Formula (1) is two coordination structures, and formula (2) is the three-fold coordination structure, and wherein R1, R2, R3, R4, R5, R6 represent the alkane or the aromatic hydrocarbon group of different chain length and structure, and A1, A2, A3 represent above-mentioned electron rich group.
Alkaline matter in preparing method's step 3 is oxyhydroxide or organic amine or ammoniacal liquor, and organic amine is triethylamine or trolamine or diethylolamine.
Oxygenant described in preparing method's step 4 is a hydrogen peroxide.
Described high speed homogenization equipment is the high-shear homogenizer with slit shear constitution, and its rotating speed is 5000-25000 rev/min.
Described hypergravity conversion unit is a RPB type reactor drum, and speed range is at 800-2000 rev/min, and reaction mass leans on centrifugal action to produce at filling surface and shears dispersion.
Said non-polar oil is meant solvent treatment type lubricant base, or the hydrogenation lubricant base, or positive structure or isoparaffin solvent etc.
Among the present invention, but oil soluble coordination organic cpds at first with inorganic cerium salt generation coordination chemistry, generate the oil soluble cerium complexes, thereby solved transfer and cerium salt the homodisperse problem organic phase of cerium salt from inorganic to organic phase; The organic cerium complexes of oil soluble trivalent is generating the solid oxidation cerium in high shear field environment generation oxidizing reaction; High shear field has guaranteed that the solid oxidation cerium particle diameter that generates is little; And be evenly distributed; And but the coordination organic cpds acts on cerium all the time mutually in entire reaction course, has guaranteed that the nano-cerium oxide solids promptly obtain reliable surface treatment when generating.In whole preparation process, but the coordination organic cpds is the part with inorganic cerium reactant salt, is again the surface treatment agent of cerium oxide nano particle, and surface treatment accomplishes when cerium oxide nano particle generates, and treatment effect is good, is easy to control; The shear field that high speed homogenization equipment, RPB type hypergravity conversion unit provide is uniform and stable; The cerium oxide nano particle size distribution that obtains is even; The particle diameter of nanoparticle has guaranteed its stable dispersion in non-polar oil within the 5-100 nanometer range; The nano-cerium oxide dispersion system solid content that obtains is higher, the highlyest can reach 40%, can the finished product be provided the liquid concentrator form; The nano-cerium oxide dispersion system can carry out through separating devices commonly used such as whizzers with separating of water, and the whole preparation process flow process is simple, does not relate to specific installation, and aftertreatment is easy, can not produce pressure to environment, and the easy realization of industrial amplification is produced.
Characteristics of the present invention are: adopt high-shears such as high speed homogenization equipment, RPB type hypergravity conversion unit, strong dispersion reactor to combine with nanoparticle surface in-situ treatment technology; High-shear, strong dispersion reactor have guaranteed that the cerium oxide nano solid grain size that obtains is even; But the coordination organic cpds is the part of inorganic cerium salt; Be again that cerium oxide is received material particulate surface treatment agent; Thereby guaranteed the reliable treatments on nano-cerium oxide surface, the nano-cerium oxide particle diameter that finally obtains is even, in non-polar oil, can form stable dispersion system.In addition, preparation technology's flow process of nano-cerium oxide dispersion system of the present invention is brief, and aftertreatment is simple, can not produce detrimentally affect to environment, and institute's use equipment all is existing industrialization products, and easy realization of industrial is amplified production.
Embodiment
Embodiment 1:
Get nitrogenous compound (1) (wherein R is that carbonatoms is 10 alkyl),
Being dissolved in non-polar oil by 10% mass concentration is in the normal hexane solvent, and about 40 ℃ of adjustment high speed homogenization built-in temperatures are sheared rotating speed at 10000 rev/mins; Add the cerous compounds aqueous solution (5% mass concentration) with mole such as compound (1), homogeneous 60 minutes adds ammoniacal liquor; Liquid pH value is reached about 9, is to add hydrogen peroxide, homogeneous 60 minutes at 2: 1 by the mol ratio of oxygenant and the inorganic cerium salt of trivalent; Separate and remove water layer, obtain the normal hexane system of nano-cerium oxide particle.
Show that with nano particle size appearance test result the diameter of gained cerium oxide particles is the 54-83 nanometer; Use centrifugal radius be 10 centimetres whizzer 4000 rev/mins centrifugal 30 minutes down, do not have obvious solid precipitation and demixing phenomenon.
Embodiment 2:
Get sulfocompound (2) (wherein R is that carbonatoms is 15 alkyl), by 10% quality
It is in the normal hexane solvent that concentration is dissolved in non-polar oil, and about 40 ℃ of adjustment high speed homogenization built-in temperatures are sheared rotating speed at 10000 rev/mins; Add the cerous compounds aqueous solution (5% mass concentration) with mole such as compound (2), homogeneous 60 minutes adds ammoniacal liquor; Liquid pH value is reached about 9, is to add hydrogen peroxide, homogeneous 60 minutes at 2: 1 by the mol ratio of oxygenant and the inorganic cerium salt of trivalent; Separate and remove water layer, obtain the normal hexane system of nano-cerium oxide particle.
Show that with nano particle size appearance test result the diameter of gained cerium oxide particles is the 25-58 nanometer; Use centrifugal radius be 10 centimetres whizzer 4000 rev/mins centrifugal 30 minutes down, do not have obvious solid precipitation and demixing phenomenon.
Embodiment 3:
Get oxygenatedchemicals (3) (wherein R is that carbonatoms is 8 alkyl), being dissolved in non-polar oil by 10% mass concentration is in the normal hexane solvent, about 40 ℃ of adjustment high speed homogenization built-in temperatures,
Shear rotating speed at 10000 rev/mins, wait the mole adding cerous compounds aqueous solution (5% mass concentration), homogeneous 60 minutes with compound (3); Add ammoniacal liquor; Liquid pH value is reached about 9, is to add hydrogen peroxide, homogeneous 60 minutes at 2: 1 by the mol ratio of oxygenant and the inorganic cerium salt of trivalent; Separate and remove water layer, obtain the normal hexane system of nano-cerium oxide particle.
Show that with nano particle size appearance test result the diameter of gained cerium oxide particles is the 55-98 nanometer; Use centrifugal radius be 10 centimetres whizzer 4000 rev/mins centrifugal 30 minutes down, do not have obvious solid precipitation and demixing phenomenon.
Embodiment 4:
Get oxygenatedchemicals (4) (wherein R is that carbonatoms is 10 alkyl), by 10% quality
It is in the normal hexane solvent that concentration is dissolved in non-polar oil, and about 40 ℃ of adjustment high speed homogenization built-in temperatures are sheared rotating speed at 10000 rev/mins; Add the cerous compounds aqueous solution (5% mass concentration) with mole such as compound (4), homogeneous 60 minutes adds ammoniacal liquor; Liquid pH value is reached about 9, is to add hydrogen peroxide, homogeneous 60 minutes at 2: 1 by the mol ratio of oxygenant and the inorganic cerium salt of trivalent; Separate and remove water layer, obtain the normal hexane system of nano-cerium oxide particle.
Show that with nano particle size appearance test result the diameter of gained cerium oxide particles is the 33-58 nanometer; Use centrifugal radius be 10 centimetres whizzer 4000 rev/mins centrifugal 30 minutes down, do not have obvious solid precipitation and demixing phenomenon.
Embodiment 5:
Press embodiment 1, get nitrogenous compound (1), being dissolved in non-polar oil by 25% mass concentration is in the 150SN MO; About 50 ℃ of adjustment high speed homogenization built-in temperatures are sheared rotating speed at 5000 rev/mins, wait the mole adding cerous compounds aqueous solution (15% mass concentration) with compound (1); Homogeneous 30 minutes adds triethylamine, and liquid pH value is reached about 9; Mol ratio by oxygenant and the inorganic cerium salt of trivalent is 1.5: 1 adding hydrogen peroxide; Homogeneous 90 minutes separates and removes water layer, obtains the 150SN MO system of nano-cerium oxide particle.
The diameter of gained cerium oxide particles is the 5-34 nanometer.
Embodiment 6:
Press embodiment 1, get nitrogenous compound (1), be dissolved in non-polar oil promptly in No. 2 hydrogenation lubricant bases by 40% mass concentration; About 60 ℃ of adjustment high speed homogenization built-in temperatures are sheared rotating speed at 15000 rev/mins, wait mole adding cerous compounds methanol solution (25% mass concentration) with compound (1); Homogeneous 90 minutes adds trolamine, and liquid pH value is reached about 9; Mol ratio by oxygenant and the inorganic cerium salt of trivalent is 2.5: 1 adding hydrogen peroxide; Homogeneous 30 minutes separates and removes methyl alcohol, obtains No. 2 hydrogenated oil systems of nano-cerium oxide particle.
The diameter of gained cerium oxide particles is the 12-45 nanometer.
Embodiment 7:
Press embodiment 1, get nitrogenous compound (1), being dissolved in non-polar oil by 50% mass concentration is in the diesel oil; About 50 ℃ of adjustment high speed homogenization built-in temperatures are sheared rotating speed at 20000 rev/mins, add cerous compounds ethanolic soln (30% mass concentration) with compound (1) by 1: 2 mol ratio; Homogeneous 120 minutes adds diethylolamine, and liquid pH value is reached about 9; Mol ratio by oxygenant and the inorganic cerium salt of trivalent is 2: 1 adding hydrogen peroxide; Homogeneous 90 minutes separates and removes ethanol, obtains the diesel oil system of nano-cerium oxide particle.
The diameter of gained cerium oxide particles is the 8-35 nanometer.
Embodiment 8:
Press embodiment 1, get nitrogenous compound (1), being dissolved in non-polar oil by 40% mass concentration is in the kerosene; About 50 ℃ of adjustment high speed homogenization built-in temperatures are sheared rotating speed at 25000 rev/mins, add the cerous compounds aqueous solution (30% mass concentration) with compound (1) by 1: 3 mol ratio; Homogeneous 60 minutes adds sodium hydroxide, and liquid pH value is reached about 9; Mol ratio by oxygenant and the inorganic cerium salt of trivalent is 2: 1 adding hydrogen peroxide; Homogeneous 120 minutes separates to remove and anhydrates, and obtains the kerosene system of nano-cerium oxide particle.
The diameter of gained cerium oxide particles is the 25-65 nanometer.
Embodiment 9:
Press embodiment 8, replace high-shear homogenizer with RPB type supergravity reactor, temperature is about 40 ℃ in the adjustment supergravity reactor, shears rotating speed at 800 rev/mins.
The diameter of gained cerium oxide particles is the 5-38 nanometer.
Embodiment 10:
Press embodiment 9, temperature is about 50 ℃ in the adjustment supergravity reactor, shears rotating speed at 1500 rev/mins.
The diameter of gained cerium oxide particles is the 5-28 nanometer.
Embodiment 11:
Press embodiment 9, temperature is about 60 ℃ in the adjustment supergravity reactor, shears rotating speed at 2000 rev/mins.
The diameter of gained cerium oxide particles is the 5-21 nanometer.
Embodiment 12:
Press embodiment 2, get nitrogenous compound (2), being dissolved in non-polar oil by 25% mass concentration is in the 150SN MO; About 50 ℃ of adjustment high speed homogenization built-in temperatures are sheared rotating speed at 5000 rev/mins, wait the mole adding cerous compounds aqueous solution (15% mass concentration) with compound (1); Homogeneous 30 minutes adds triethylamine, and liquid pH value is reached about 9; Mol ratio by oxygenant and the inorganic cerium salt of trivalent is 1.5: 1 adding hydrogen peroxide; Homogeneous 90 minutes separates and removes water layer, obtains the 150SN MO system of nano-cerium oxide particle.
The diameter of gained cerium oxide particles is the 36-89 nanometer.
Embodiment 13:
Press embodiment 2, get nitrogenous compound (2), being dissolved in non-polar oil by 50% mass concentration is in the diesel oil; About 50 ℃ of adjustment high speed homogenization built-in temperatures are sheared rotating speed at 20000 rev/mins, add cerous compounds ethanolic soln (30% mass concentration) with compound (1) by 1: 2 mol ratio; Homogeneous 120 minutes adds diethylolamine, and liquid pH value is reached about 9; Mol ratio by oxygenant and the inorganic cerium salt of trivalent is 2: 1 adding hydrogen peroxide; Homogeneous 90 minutes separates and removes ethanol, obtains the diesel oil system of nano-cerium oxide particle.
The diameter of gained cerium oxide particles is the 18-57 nanometer.
Embodiment 14:
Press embodiment 13, replace high-shear homogenizer with RPB type supergravity reactor, temperature is about 40 ℃ in the adjustment supergravity reactor, shears rotating speed at 1200 rev/mins.
The diameter of gained cerium oxide particles is the 5-23 nanometer.
Embodiment 15:
Press embodiment 3, get nitrogenous compound (3), be dissolved in non-polar oil promptly in No. 2 hydrogenation lubricant bases by 40% mass concentration; About 60 ℃ of adjustment high speed homogenization built-in temperatures are sheared rotating speed at 20000 rev/mins, wait the mole adding cerous compounds aqueous solution (25% mass concentration) with compound (3); Homogeneous 90 minutes adds trolamine, and liquid pH value is reached about 9; Mol ratio by oxygenant and the inorganic cerium salt of trivalent is 2.5: 1 adding hydrogen peroxide; Homogeneous 60 minutes separates to remove and anhydrates, and obtains No. 2 hydrogenated oil systems of nano-cerium oxide particle.
The diameter of gained cerium oxide particles is the 35-95 nanometer.
Embodiment 16:
Press embodiment 15, replace high-shear homogenizer with RPB type supergravity reactor, temperature is about 40 ℃ in the adjustment supergravity reactor, shears rotating speed at 1200 rev/mins.
The diameter of gained cerium oxide particles is the 5-20 nanometer.
Embodiment 17:
Press embodiment 4, get nitrogenous compound (4), being dissolved in non-polar oil by 40% mass concentration is in the kerosene; About 50 ℃ of adjustment high speed homogenization built-in temperatures are sheared rotating speed at 25000 rev/mins, add the cerous compounds aqueous solution (30% mass concentration) with compound (4) by 1: 3 mol ratio; Homogeneous 60 minutes adds sodium hydroxide, and liquid pH value is reached about 9; Mol ratio by oxygenant and the inorganic cerium salt of trivalent is 2: 1 adding hydrogen peroxide; Homogeneous 120 minutes separates to remove and anhydrates, and obtains the kerosene system of nano-cerium oxide particle.
The diameter of gained cerium oxide particles is the 26-95 nanometer.
Embodiment 18:
Press embodiment 17, replace high-shear homogenizer with RPB type supergravity reactor, temperature is about 40 ℃ in the adjustment supergravity reactor, shears rotating speed at 2000 rev/mins.
The diameter of gained cerium oxide particles is the 5-22 nanometer.
Claims (6)
1. cerium oxide nano particle preparation method is characterized in that:
Concrete preparation method is:
(1) but, the mass concentration of coordination organic cpds with 10-50% is dissolved in the non-polar oil, and this solution is added in high speed homogenization equipment or the hypergravity conversion unit;
(2), the aqueous solution or the methanol solution or the ethanolic soln of preparation Cerium II Chloride or the inorganic cerium salt of cerous nitrate trivalent, the mass concentration that makes the inorganic cerium solution of trivalent is 5-30%;
(3), the inorganic cerium solution of trivalent is joined in high speed homogenization equipment or the hypergravity conversion unit; But the mol ratio of the inorganic cerium salt of coordination organic cpds and trivalent is 1～3: 1, and 40-60 ℃ of opertaing device temperature sheared 800-25000 rev/min of rotating speed; Reaction times is 30-120 minute; After the end, add alkaline matter, make the pH value of liquid make it reach 8～10;
(4), in the liquid of equipment, add oxygenant and carry out oxidizing reaction; The mol ratio of the inorganic cerium salt of oxygenant and trivalent is 1.5-2.5: 1; Reaction times 30-120 minute, shear 800-25000 rev/min of rotating speed, after the end; The centrifugal water layer of removing promptly obtains the cerium oxide nano particle of particle diameter in the 5-100 nanometer;
But described coordination organic cpds is the compound that comprises the electron rich group of nitrogen or oxygen or sulfur heteroatom in the molecular structure; Contain long chain alkane structure in the molecule simultaneously greater than 8 carbon; And these electron rich groups can form stable coordination compound through coordination with cerium atom; Guarantee its favorable solubility in non-polar oil, the general formula of this compounds is following:
Formula (1) is two coordination structures, and formula (2) is the three-fold coordination structure, and wherein R1, R2, R3, R4, R5, R6 represent the alkane or the aromatic hydrocarbon group of different chain length and structure, and A1, A2, A3 represent above-mentioned electron rich group.
2. a kind of cerium oxide nano particle preparation method according to claim 1 is characterized in that: the alkaline matter in preparing method's step (3) is oxyhydroxide or organic amine, and organic amine is triethylamine or trolamine or diethylolamine.
3. a kind of cerium oxide nano particle preparation method according to claim 1 is characterized in that: the oxygenant described in preparing method's step (4) is a hydrogen peroxide.
4. a kind of cerium oxide nano particle preparation method according to claim 1 is characterized in that: described high speed homogenization equipment is the high-shear homogenizer with slit shear constitution, and its rotating speed is 5000-25000 rev/min.
5. a kind of cerium oxide nano particle preparation method according to claim 1; It is characterized in that: described hypergravity conversion unit is a RPB type reactor drum; Speed range is at 800-2000 rev/min, and reaction mass leans on centrifugal action to produce at filling surface and shears dispersion.
6. a kind of cerium oxide nano particle preparation method according to claim 1 is characterized in that: said non-polar oil is meant solvent treatment type lubricant base, or the hydrogenation type lubricant base, or positive structure or isoparaffin solvent.
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| CN111434379B (en) * | 2019-01-11 | 2021-10-29 | 北京化工大学 | Oil-soluble monodisperse nano cerium dioxide catalyst, preparation method and application |
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